EP4005016B1 - Zylindrische anodenfreie festkörperbatterie mit einer pseudofesten lithiumgelschicht - Google Patents

Zylindrische anodenfreie festkörperbatterie mit einer pseudofesten lithiumgelschicht

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Publication number
EP4005016B1
EP4005016B1 EP20754569.0A EP20754569A EP4005016B1 EP 4005016 B1 EP4005016 B1 EP 4005016B1 EP 20754569 A EP20754569 A EP 20754569A EP 4005016 B1 EP4005016 B1 EP 4005016B1
Authority
EP
European Patent Office
Prior art keywords
layer
dendrite
anode
current collector
lithium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP20754569.0A
Other languages
English (en)
French (fr)
Other versions
EP4005016A1 (de
Inventor
Ken Ogata
Yang Yang
Hajime Hoshi
Jungho Kim
Masatsugu Nakano
Hiroshi Imoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Terawatt Technology Inc
Original Assignee
Terawatt Technology Inc
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Publication date
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Publication of EP4005016A1 publication Critical patent/EP4005016A1/de
Application granted granted Critical
Publication of EP4005016B1 publication Critical patent/EP4005016B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0422—Cells or battery with cylindrical casing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0583—Construction or manufacture of accumulators with folded construction elements except wound ones, i.e. folded positive or negative electrodes or separators, e.g. with "Z"-shaped electrodes or separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • H01M4/0447—Forming after manufacture of the electrode, e.g. first charge, cycling of complete cells or cells stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • H01M2300/0097—Composites in the form of layered products, e.g. coatings with adhesive layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • lithium ions migrate from battery's cathode to the battery's anode through a separator located between the cathode and anode.
  • a separator located between the cathode and anode.
  • lithium ions become inserted into the material functioning as the anode.
  • lithium ions may also plate onto a surface of the anode facing the separator.
  • the nucleation energy associated with the anode may encourage lithium ions to plate on top of other lithium that has already plated onto the anode (rather than plating in a roughly even film across the surface of the anode). These pools of lithium can form dendrites.
  • a dendrite can be a protrusion of lithium metal that extends away from the surface of the anode towards the separator. Over time (e.g., through multiple charge and discharge cycles), dendrites may grow to such a length that the dendrite pierces the separator and directly electrically connects (i.e. short circuits) the cathode with the anode. Such an electrical connection can result in destruction of the battery and possibly serious side-effects, such as overheating and fire.
  • KR-A-2019/0001556 describes a lithium secondary battery which is made of a cathode-free battery and formed with lithium metal on a cathode current collector by charging.
  • KR-A-2019/0079534 A describes a lithium secondary battery assembled in a form without a negative electrode active material.
  • the present invention is directed to a method for manufacturing a cylindrical anti-dendrite anode-free solid-state battery as well as to a cylindrical anti-dendrite anode-free solid-state battery, as defined in the appended claims.
  • Various embodiments are described related to a method for creating a cylindrical anti-dendrite anode-free solid-state battery.
  • a method for creating a cylindrical anti-dendrite anode-free solid-state battery is described.
  • the method may comprise attaching a cathode layer with a cathode current collector layer.
  • the method may comprise layering an anti-dendrite layer between an anode current collector layer and the cathode layer.
  • the method may comprise creating a layered stack that comprises a dry separator layer, the cathode layer layered with the cathode current collector layer, and the anti-dendrite layer layered with the anode current collector layer.
  • the dry separator layer may be located between the cathode layer and the anti-dendrite layer.
  • the method may comprise rolling the layered stack into a cylindrical jelly roll.
  • the method may comprise inserting the rolled layered stack into a pouch.
  • the method may comprise permeating a liquid electrolyte mixture into the pouch.
  • the liquid electrolyte mixture may permeate the dry separator layer and the liquid electrolyte mixture may comprise a salt and a solvent.
  • the method may comprise applying pressure to the pouch after permeating the liquid electrolyte mixture.
  • the method may comprise, while applying pressure to the pouch, applying heat to the pouch.
  • the heat at least in part may cause the liquid electrolyte mixture that permeates the dry separator layer to become a gel.
  • the method may comprise removing the rolled layered stack from the pouch after applying the pressure and the heat.
  • the method may comprise inserting the rolled layered stack that has been removed from the pouch into a cylindrical battery cell canister.
  • Embodiments of such a method may include one or more of the following features: the liquid electrolyte mixture may further comprise a polymer additive and a cross-linker additive that may cause the liquid electrolyte mixture to become the gel when the heat is applied.
  • a first adhesive layer may be attached to the dry separator layer such that the first adhesive layer may be located between the dry separator layer and the cathode layer.
  • a second adhesive layer may be attached to the dry separator layer such that the second adhesive layer may be located between the dry separator layer and the anti-dendrite layer.
  • the method may further comprise inserting the pouch into a cylindrical press module, the cylindrical press module comprising: a compressible material wrapped around a curved edge of the pouch.
  • the method may further comprise inserting a temperature probe to monitor temperature between the pouch and the cylindrical press module.
  • the heat may be applied through the compressible material wrapped around the curved edge of the pouch.
  • the heat applied may be between 150°C and 250°C.
  • a presence of the anti-dendrite layer may cause a nucleation barrier to be decreased in energy for lithium ions to deposit onto the anode current collector layer.
  • the anti-dendrite layer may be between 0.05 micrometers and 10 micrometers in thickness.
  • the anti-dendrite layer may comprise one or more materials selected from the group consisting of: carbon black; acetylene black; ketchen black; silver; zinc; gold; bismuth; tin; polyvinylidene fluoride (PVDF); polymide (PI); polyacrylic acid (PAA); and carboxymethyl cellulose styrene-butadiene rubber (CMC-SBR).
  • the method may further comprise depositing an interfacial bonding layer onto the anode current collector layer.
  • a cylindrical anti-dendrite anode-free solid-state battery may comprise a cathode layer.
  • the battery may comprise a cathode current collector layer attached with the cathode layer.
  • the battery may comprise an anode current collector layer.
  • the battery may comprise an anti-dendrite layer located between the anode current collector layer and the cathode layer.
  • the battery may comprise a lithium gel separator layer located between the cathode layer and the anti-dendrite layer.
  • the battery may comprise a canister into which the cathode layer, the cathode current collector layer, the anode current collector layer, the anti-dendrite layer, and the lithium gel separator layer may be inserted.
  • the lithium gel separator layer may comprise: a scaffold material; a lithium salt; a solvent; and two or more additives.
  • the two or more additives may comprise a polymer additive and a cross-linker additive.
  • the polymer additive and the cross-linker additive may cause the solvent and the lithium salt to form a gel when exposed to heat.
  • the device further comprises an interfacial bonding layer deposited onto the anode current collector layer. A first amount of adhesion between the interfacial bonding layer and the anode current collector layer is greater than a second amount of adhesion between the interfacial layer and the anti-dendrite layer.
  • the anti-dendrite layer may comprise one or more materials selected from the group consisting of: carbon black; acetylene black; ketchen black; silver; zinc; gold; bismuth; tin; polyvinylidene fluoride (PVDF); polymide (PI); polyacrylic acid (PAA); and carboxymethyl cellulose styrene-butadiene rubber (CMC-SBR).
  • the anti-dendrite layer may be between 0.05 micrometers and 10 micrometers in thickness. A presence of the anti-dendrite layer may cause a nucleation barrier to be decreased in energy for lithium ions to deposit onto the anode current collector layer.
  • An anti-dendrite layer in combination with a lithium gel separator layer can inhibit the growth of dendrites while not increasing the thickness of the battery cell by a large amount.
  • An anti-dendrite layer may be coated directly onto an anode current collector of an anode-free solid state battery (SSB).
  • SSB solid state battery
  • the anode current collector which can be a copper foil, may effectively function as both the anode and the anode current collector.
  • the anti-dendrite layer may decrease the nucleation energy needed for lithium ions to deposit as lithium metal onto the surface of the anode current collector that is in contact with the anti-dendrite layer.
  • lithium may tend to deposit in a roughly even film across the surface of the anode current collector.
  • the anti-dendrite layer may be in direct contact with a lithium gel separator layer.
  • the lithium gel separator layer may serve multiple functions. First, the lithium gel separator layer can function as a solid-state electrolyte to facilitate movement of lithium ions between the cathode and the anode. The lithium gel separator layer also serves as a separator to prevent a direct electrical connection between the cathode and anode. The lithium gel separator layer further can have characteristics that further inhibit dendrite growth.
  • FIG. 1 illustrates an embodiment of a layer stack 100 of an anode-free solid-state battery having a lithium gel separator layer and an anti-dendrite layer.
  • Layer stack 100 can include: cathode current collector 110; cathode 120; lithium gel separator layer 130; anti-dendrite layer 140; and anode current collector 150.
  • Cathode current collector 110 may be a conductive film that is layered with cathode 120.
  • Cathode current collector 110 may, for example, be an aluminum foil. Other forms of conductive foils are possible.
  • Cathode 120 may, for example, be NCA (Nickel-Cobalt-Aluminum Oxide) or NCM (nickel-manganese-cobalt).
  • Cathode 120 may have a first surface in direct contact with cathode current collector 110, an opposite surface of cathode 120 can be in direct contact with lithium gel separator layer 130.
  • Lithium gel separator layer 130 can function as a solid-state electrolyte (in the form of a gel) to facilitate movement of lithium ions between cathode 120 and anode current collector 150.
  • Lithium gel separator layer 130 also serves as a separator to prevent a direct electrical connection between cathode 120 and anode current collector 150.
  • Lithium gel separator layer 130 can have characteristics that further inhibit dendrite growth.
  • Lithium gel separator layer 130 may be initially at least partially in liquid form. After assembly, a process may be applied to convert the liquid to a gel form. Such a process may involve the application of pressure, heat, or both. Further detail regarding lithium gel separator layer 130 is provided in relation to FIG. 3A .
  • a second key characteristic of anti-dendrite layer 140 is that an amount of adhesion between anti-dendrite layer 140 and anode current collector 150 is less than an amount of adhesion between anti-dendrite layer 140 and lithium gel separator layer 130. By adhesion being less between the surfaces of anti-dendrite layer 140 and anode current collector 150, lithium is encouraged to plate between anti-dendrite layer 140 and anode current collector 150 as opposed to between lithium gel separator layer 130 and anti-dendrite layer 140.
  • Anti-dendrite layer 140 may be relatively thin. For instance, anti-dendrite layer 140 may be between 0.05 ⁇ m and 10 ⁇ m. In some embodiments, anti-dendrite layer 140 may be deposited as a film on a surface of anode current collector 150. Anti-dendrite layer 140 may be made of one or more of the following materials: carbon black; acetylene back black; silver; zinc; gold; bismuth; tin; polyvinylidene fluoride (PvDF); polymide (PI); polyacrylic acid (PAA); and carboxymethyl cellulose styrene-butadiene rubber (CMC-SBR).
  • PvDF polyvinylidene fluoride
  • PI polymide
  • PAA polyacrylic acid
  • CMC-SBR carboxymethyl cellulose styrene-butadiene rubber
  • Anti-dendrite layer 140 may also be formed using alloys of silver, zinc, gold, bismuth, and tin. While anti-dendrite layer 140 may be formed from a single type of material; multiple materials indicated may be used to form anti-dendrite layer 140.
  • Anode current collector 150 can function as both the anode and the anode current collector.
  • anode currently collector 150 is a conductive foil, such as a copper foil. Without anti-dendrite layer 140 being present, anode current collector 150 may exhibit a higher nucleation energy that tends to cause lithium to pool rather than deposit as a film during charging of the battery cell.
  • FIG. 2 illustrates another embodiment of a layer stack 200 of an anode-free solid-state battery having lithium gel separator layers and anti-dendrite layers.
  • multiple sets of layers may be layered together to increase the charge capacity of the battery cell.
  • layers 110 through 150 are as detailed in relation to FIG. 1 .
  • anti-dendrite layer 210 is layered on an opposite side of anode current collector 150 from anti-dendrite layer 140.
  • a second lithium gel separator layer 202 is in direct contact with anti-dendrite layer 210.
  • cathode 230 and cathode current collector 240 are layered against lithium gel separator layer 220. Additional layers may be added in the same manner as detailed in relation to FIG. 2 .
  • cathode current collector 240 may be another cathode, followed by another lithium gel separator layer, etc.
  • many sets of layers may be added to increase the charge capacity of the battery cell. While FIG. 1 shows a single stack set and FIG. 2 illustrates a double stack set; other embodiment may include may more stacks, such as 16 or more. Such layers, once together, may be sealed as part of a pouch-style battery cell.
  • FIG. 3A illustrates an embodiment of a lithium gel separator layer being formed using heat.
  • FIG. 3B illustrated herein in parallel with FIG. 3A , illustrates an embodiment of a method for creating a lithium gel separator layer.
  • the lithium gel separator layer may function as a phase-changing electrolyte, which can be used in a solid state battery.
  • a lithium gel separator layer such as lithium gel separator layer 130, can include multiple sublayers and may be created using heat. Pressure may also be used to increase the surface area of interfaces between layers of the lithium gel separator layer.
  • a non-reactive scaffold may be formed at block 350.
  • scaffolding material 305 may be polyethylene (PE) or polyethylene oxide (PEO).
  • Scaffolding material 305 may be permeable such that a liquid, such as an electrolyte liquid can be permeated, injected, or otherwise introduced to scaffolding material 305.
  • the physical structure of scaffolding material 305 may create gaps that can be filled with liquid.
  • scaffolding material 305 may have a porosity of between 10% and 90%, into which a liquid can be introduced.
  • the specific physical structure may be honeycomb structure, spider-web structure, or some other pattern or random porous physical structure that allows liquid to fill empty spaces within scaffolding material 305.
  • the scaffolding layer may between 1 ⁇ m and 100 ⁇ m thick. In some embodiments, the scaffolding layer is 15 ⁇ m thick.
  • a first adhesive layer may be attached to the non-reactive scaffold.
  • a second adhesive layer may be attached to an opposite side of the non-reactive scaffold. Therefore, scaffolding material 305 may be located between two adhesive layers 310. Together, these three layers may form dry separator layer 300 in which an electrolyte has not yet been introduced.
  • Each of adhesive layers 310 may include either PvDF, PI, PAA, or CMC-SBR. Such materials can function as an adhesive bonder. Therefore, adhesive layers 310 can serve to increase the amount of adhesion between scaffolding material 305, cathode 120, and anti-dendrite layer 140. An amount of adhesion between lithium gel separator layer 130 and anti-dendrite layer 140, at least in part due to an adhesion layer, may be greater than an amount of adhesion between anti-dendrite layer 140 and anode current collector 150.
  • a ceramic may be added to one or both adhesive layers that improves lithium ion transport and can help discourage dendrite formation.
  • Such ceramics can include: MgO, PZT, BaTiO3, SBT, BFO, LATSPO, LISICON, LICGC, LAGP, LLZO, LZO, LAGTP, LiBETI, LiBOB, LiTf, LiTF, LLTO, LLZP, LTASP, and LTZP.
  • Each of adhesive layers 310 may be between 1-500 um in thickness. Using ceramics within the adhesive layers can decrease ionic-conductivity.
  • Li-ion conductor ceramic may still decrease ionic-conductivity (compared with liquid), but can secure higher ionic-conductivity compared with other ceramics.
  • the advantage of a ceramic being able to prevent a short-circuit and to decrease overall cell failure rate may out-weigh the drawback of the decreased ionic conductivity.
  • a liquid electrolyte mixture may be created.
  • the liquid electrolyte mixture may include: a lithium salt; a solvent; and additives.
  • the salt may be LIFSI, LITFSI, or LiPF6.
  • the concentration of the salt may be between 1.0 to 4.0 mole per liter.
  • the lithium salt may allow the lithium liquid to function as an electrolyte.
  • the solvent may be: dimethyl carbonate (DMC), dimethoxyethane (DME), diethyl carbonate (DEC), dioxolane (DOL), bis trifluoroethyl ether (BTFE), ehtyl methyl carbonate (EMC), or ethylene carbonate (EC).
  • the solvent may function to dissolve the salt.
  • the additives may include the compounds within the lithium liquid that causes a transition from a liquid to a gel when heat is applied.
  • the additives comprise a polymer and cross-linker.
  • the cross-linker ignites and causes further polymerization of the polymer and the solvent. Since the lithium salt is evenly distributed throughout the solvent, when the gel is formed, the lithium salt will be evenly distributed throughout the gel.
  • the one or more additives may include CsPF6, FEC (fluoroethylene carbonate), polycarbonate (PC), or LiNO3.
  • the additive may have a concentration of 0.01-4.0 moles per liter.
  • the additives includes the polymer additive and the cross-linker additive may be mixed into the lithium liquid before the lithium liquid is permeated throughout the non-reactive scaffolding.
  • lithium salt and solvent may be 4 M of LiFSI dissolved in DME, to which the additives can be added.
  • Table 1 indicates a combination of polymer additive, cross-linker additive, and the relative concentrations that can be used of the polymer additive and cross-linker additive.
  • one or more additional additives may also function to reduce side reactions.
  • a purpose of adding an additive can be to help form LiF, namely solid electrolyte interphase (SEI), which can prevent Li metal from having various side reactions.
  • SEI solid electrolyte interphase
  • dry separator layer 300 may be layered with other battery cell layers in the place of lithium gel separator layer 130.
  • a liquid electrolyte may be added, then heat and pressure may be applied.
  • the liquid electrolyte mixture may be permeated into the non-reactive scaffold.
  • Arrow 315 represents that lithium liquid is permeated throughout scaffolding material 305 to create lithium liquid-permeated scaffolding material 320.
  • the lithium liquid may permeate the scaffolding material when left submerged at atmospheric pressure for a duration of time, such as between 6 hours and 24 hours. This step may be performed after the dry separator layer has been assembled as part of a battery cell.
  • the liquid electrolyte which can be a lithium liquid, may be composed of materials that after permeating into the voids within the scaffolding material and then subjected to heat, causing the lithium liquid at least partially solidify, such as into a gel.
  • Such an arrangement allows for a lithium gel separator layer to be initially created as a dry separator layer then for lithium liquid to be permeated throughout the scaffolding material and transitioned into being a gel after the battery cell is housed within a housing (e.g., a pouch cell).
  • a housing e.g., a pouch cell
  • pressure is also applied, the purpose of the pressure may be to crease the amount of contact at various interfaces within the layered stack.
  • block 375 may be performed in which pressure, heat, or both may be applied, as indicated by arrow 325.
  • pressure may first be applied at room temperature, at a force of 100 N/cm 2 for a duration of between 60 and 120 seconds.
  • a heat press process may then be performed at a temperature of between 100°C - 110°C at a force of between 100 - 500 N/cm 2 for a duration of between 60 and 120 seconds.
  • the heat applied to lithium gel separator layer 301 may cause lithium liquid-permeated scaffolding material 320 to transition into pseudo-solid lithium gel layer 330.
  • pressure may assist the process or may help increase the surface area of interfaces between layers of the lithium gel separator layer and/or other layers of the battery cell.
  • Lithium gel separator layer 302 may then be finally formed.
  • FIG. 4 illustrates an embodiment of a method 400 for manufacturing a pouch-style battery cell that contains an anode-free solid-state battery having a lithium gel separator layer and an anti-dendrite layer.
  • an anti-dendrite layer may be layered onto an anode current collector.
  • the anti-dendrite layer may be as detailed in relation to anti-dendrite layer 140 of FIG. 1 .
  • the anode current collector may be as detailed in relation to anode current collector 150 of FIG. 1 .
  • a three-part lithium gel separator layer may be created.
  • the lithium gel separator layer may be in the form of a dry separator layer. That is, liquid electrolyte, such as lithium liquid, has not yet been injected into the scaffolding layer as detailed in relation to FIG. 3A .
  • the scaffolding material at block 410 has been permeated with the liquid.
  • the lithium gel separator layer in which the lithium liquid may be present or not yet introduced, may be layered onto anti-dendrite layer at block 415.
  • the amount of adhesion between the lithium gel separator layer and the anti-dendrite layer may be greater than the amount of adhesion between the anti-dendrite layer and the anode current collector. In some instances, the amount of adhesion between the lithium gel separator layer and the anti-dendrite layer may be greater than the amount of adhesion between the anti-dendrite layer and the anode current collector after the heating and pressing of block 430.
  • the cathode layer may be layered onto the lithium gel separator layer (of which the gel is still in the form of a liquid or has not yet been introduced to the scaffolding material).
  • the cathode collector layer may be layered onto the cathode layer. In some embodiments, block 425 may be performed, then the combined cathode and cathode current collector layers may be layered onto the lithium gel separator layer (of which the gel is still in the form of a liquid or has not yet been introduced to the scaffolding material) at block 420.
  • blocks 405-425 may be repeated multiple times to create multiple layer stacks for a solid state battery cell. For instance, 16 sets of layers may be created in a stack set similar to detailed in relation to FIG. 2 . Such an arrangement allows for the anode current collector and cathode current collector to be in contact with anti-dendrite layers and cathodes, respectively, on opposite sides.
  • the one or more layer stacks may be packaged in a pouch cell.
  • the lithium liquid (or other form of liquid electrolyte), assuming it was introduced at block 410, may still be in liquid form.
  • the layers stacks may be vacuum sealed within the pouch cell to remove excess air.
  • the pouch cell may be made of a flexible material, such as plastic, that can allow the pouch to expand and be compressed. If the lithium liquid was not permeated throughout the scaffolding layer at block 410, the lithium liquid may be introduced within the pouch cell when packaging is being performed (or before or after) at block 432. The lithium liquid may then permeate into the scaffolding layer of the dry separator layer.
  • one or more processes of heat, pressure, or both may be applied to the packaged pouch cell.
  • This process can perform multiple functions: 1) block 435 may increase the amount of physical contact between adjacent layers of the battery cell; 2) block 435 may cause the lithium liquid to convert to a lithium gel; and 3) block 435 may create adhesion between the anti-dendrite layers and the lithium gel layers that is greater than the amount of adhesion between the anti-dendrite layers and the anode current collectors.
  • pressure may first be applied at room temperature, at a force of between 80 and 120 N/cm 2 for a duration of between 60 and 120 seconds.
  • a heat press process may then be performed at a temperature of between 80°C - 130°C at a force of between 100 - 500 N/cm 2 for a duration of between 60 and 120 seconds.
  • the pouch cell may be installed within a jig press (or some other mechanical device that applies pressure to the pouch cell).
  • the jig press may be used to apply long-term pressure to the SSB pouch cell.
  • multiple SSB pouch cells are layered and then compressed using the jig press. While in the jig press, the SSB pouch cells may be repeated charged and discharged.
  • the SSB pouch cells may be used to power a vehicle or some other form of electrically-powered device.
  • FIG. 5 illustrates an embodiment of a cylindrical battery press system 500.
  • Cylindrical battery press system 500 can include: compression mechanism 510; heating element 520; buffer material 530; cylindrical pouch battery cell (also referred to as "battery cell") 540; temperature sensor 550; support structure 560; and platform 570.
  • Embodiments of cylindrical battery press system and related systems are detailed in US Pat. App. No. 16/412,338 , entitled “Isostatic Press Devices and Processes for Cylindrical Solid-State Batteries," filed on May 14, 2019, the entire disclosure of which is hereby incorporated by reference for all purposes.
  • Other embodiments related to a system to isotropically pressurize a cylindrical battery cell are detailed in US Pat. App. No. 16/217,010 , entitled “Hydraulic Isostatic Press Processes for Solid-State Batteries", filed on December 11, 2018, the entire disclosure of which is also hereby incorporated by reference for all purposes.
  • buffer material 530 may be a sheet of buffer material in which battery cell is rolled. Therefore, the jelly-roll style battery cell may, in turn, be within a jelly-roll of buffer material. Buffer material 530 may be installed with compression mechanism 510.
  • heating element 520 may be present.
  • Heating element 520 may be generally cylindrical in shape and may have a gap along the curved sidewall that matches the gap of compression mechanism 510.
  • Heating element 520 may be a resistive heater such that when current is applied to heating element 520, heat is generated. In some embodiments, heating element 520 is capable of heating up to 250°C.
  • the amount of heat output by heating element 520 may be controlled based on the output of temperature sensor 550.
  • Temperature sensor 550 may be located between battery cell 540 and buffer material 530. Therefore, temperature sensor 550 may indicate the temperature at an external surface of battery cell 540. In some embodiments, it may be desirable for battery cell 540 to be heated to between 80°C and 120°C.
  • edge 512 can be directly fixed to support structure 560, but rather a portion of compression mechanism 510 in a vicinity of edge 512 may be fixed to support structure 560. Again here, the portion of compression mechanism 510 to edge 512 fixed to support structure 560, the more evenly distributed the pressure applied to buffer material 530 may be.
  • a dry separator layer such as dry separator layer 300
  • the dry separator layer can include two adhesive layers and a scaffolding material, such as detailed in relation to dry separator layer 300.
  • a layered stack may be created that includes the dry separator layer being layered between the cathode and the anti-dendrite layer.
  • the layered stack may include at least: the dry separator layer, the anti-dendrite layer, the anode current collector layer, the cathode layer, and the cathode current collector layer, such as illustrated to FIG. 1 (with the dry separator layer in lieu of the lithium-gel separator layer.
  • the injection of the lithium liquid may cause the scaffolding material of the dry separator layer to be permeated by the lithium liquid and become lithium-liquid permeated scaffolding material, such as lithium-liquid permeated scaffolding material 320.
  • the pouch may have any air present removed and may be sealed.
  • pressure may be applied to the pouch.
  • the pressure may be applied using a system similar to cylindrical battery press system 500.
  • a temperature probe Prior to pressure being applied, a temperature probe may be inserted such that the temperature probe is adjacent to an external surface of the pouch within the cylindrical battery press system. Pressure may then be applied by the cylindrical battery press system either manually or using a motorized or hydraulic embodiment.
  • the pressure applied may be between 100 kPa and 100 MPa. In some embodiments, pressure is applied for between 30 seconds and 1 hour.
  • heat may be applied.
  • the amount of heat applied may be between 150°C and 250°C.
  • the temperature of the pouch may be monitored using the temperature probe.
  • Heat may be applied until the battery cell is between 60°C and 150°C for a period of time, such as between 30 seconds and 1 hour.
  • the pressure, heat, or both may cause the lithium liquid that permeates the scaffolding layer to transition to being a pseudo-solid lithium gel layer. Therefore, no liquid remains within the pouch.
  • the battery cell is a solid-state battery cell (that includes a gel).
  • the heat and pressure applied at blocks 640 and 645 may additionally or alternatively increase the amount of surface area contact between one or more of the layers of the battery cell. Additionally or alternatively, the heat and pressure may increase the adhesion among two or more of the layers of the battery cell.
  • the cylindrical jelly roll that has been subjected to the heat and pressure may be removed from the pouch. No liquid may be presented because it has transitioned into a gel within the scaffolding layer.
  • the cylindrical jelly roll may be inserted into a cylindrical battery cell canister.
  • the cylindrical battery cell canister may be rigid or semi-rigid. In some embodiments, the cylindrical battery cell canister may be metal.
  • the cylindrical battery cell canister may exert pressure on the cylindrical jelly roll when the cylindrical jelly roll expands. For example, when the battery cell is charged at block 660, lithium deposition on the anode current collector can cause the battery to swell 0.5% to 3% in diameter.
  • the battery cell may repeatedly be charged and discharged to power an electric device, such as an electric vehicle (EV).
  • EV electric vehicle
  • a cylindrical battery manufactured according to method 600 may be charged to 7559 Ah, may discharge 6229 Ah, thus exhibiting an initial Columbic efficiency of 82.4%.
  • lithium deposits on an anode-current collector during charging, it may tend to deposit in pools, rather than in a roughly flat film. Since the amount of contact present between the deposited lithium and the anode current collector can be small, the electrical connection between the deposited lithium and the anode current collector may be small. Having a small or weak electrical connection between the deposited lithium and the anode current collector can cause the impedance of the battery cell to be high. A high impedance can result in reduced performance of the battery cell: that is, a battery with a low internal resistance may be able to deliver a large amount of current on demand. For some applications, like use in an electric vehicle (EV), the ability to delivery current quickly can greatly affect performance, such as the ability of the EV to accelerate. When a battery cell has a high internal resistance, current flowing through the battery cell can cause the battery to heat up, which can damage the battery cell.
  • EV electric vehicle
  • an additional layer is present within the layer stack of an anode-free solid-state battery.
  • the additional layer is situated between the anti-dendrite layer and the anode current collector.
  • This layer can be referred to as an interfacial bonding layer.
  • the interfacial bonding layer may encourage formation of lithium deposits with a high degree of surface contact between the interfacial bonding layer and the lithium deposits. Since the interfacial bonding layer has a large amount of contact with both the anode current collector and deposited lithium, the internal resistance of the battery cell can be decreased.
  • Such an interfacial bonding layer may be added to any of the embodiments detailed in relation to FIGS. 1-6 or as detailed in relation to FIGS. 7-10 .
  • An interfacial layer may be made from conductive agents and binder. In some embodiments, the interfacial layer may be between 30%-99% conductive agent; the remainder of the interfacial bonding layer may be binder (1%-70%).
  • FIG. 7 illustrates an embodiment of a layer stack 700 of an anode-free solid-state battery having a lithium gel separator layer, an anti-dendrite layer, and a interfacial bonding layer. Layer stack 700 may be as detailed in relation to FIG. 1 ., however interfacial bonding layer 710 is presented between anode current collector 150 and anti-dendrite layer 140. Interfacial bonding layer 710 may be in direct contact on a first side with anti-dendrite layer 140 and in direct contact on a second, opposite side with anode current collector 150.
  • FIG. 8 illustrates an embodiment of a layer stack 800 of an anode-free solid-state battery that indicates relative amounts of adhesion between various layers.
  • layer stack 700 of FIG. 7 may be that that the relative amount of adhesion between the layers encourages lithium metal to plate during the charging process between anti-dendrite layer 140 and interfacial bonding layer 710.
  • Interface 801 between lithium gel separator layer 130 and anti-dendrite layer 140 may have a first amount of adhesion.
  • Interface 802 between anti-dendrite layer 140 and interfacial bonding layer 710 may have a second amount of adhesion.
  • Interface 803 between interfacial bonding layer 710 and anode current collector 150 may have a third amount of adhesion.
  • FIG. 9 illustrates an embodiment 900 of a layer stack of an anode-free solid-state in which lithium ions migrate and are deposited onto the interfacial bonding layer.
  • the battery cell is being charged.
  • Charging causes lithium ions to migrate from cathode 120, through lithium gel separator layer 130, through anti-dendrite layer 140 and plate as lithium metal layer 910 between anti-dendrite layer 140 and interfacial bonding layer 710, as indicated by arrows 905.
  • Anti-dendrite layer 140 may help inhibit the growth of dendrites that could pierce lithium gel separator layer 130. Therefore, interfacial bonding layer 710 is used in conjunction with anti-dendrite layer 140.
  • lithium metal layer 910 may cause swelling in the battery cell. During a discharge cycle, lithium ion may migrate from lithium metal layer 910 to cathode 120. Swelling within the battery cell may decrease as the battery cell is discharged and lithium ions migrate to cathode layer 120.
  • FIG. 10 illustrates an embodiment of a method 1000 for manufacturing a pouch-style battery cell that contains a solid-state battery having a lithium gel separator layer, an anti-dendrite layer, and an interfacial bonding layer. It should be understood that method 1000 can be adapted in accordance with the blocks of method 600 of FIGS. 6A and 6B such that a interfacial bonding layer is manufactured as part of a cylindrical battery cell.
  • an interfacial bonding layer is deposited onto the anode current collector.
  • the anode current collector may be as detailed in relation to anode current collector 150 of FIG. 1 .
  • Block 1005 can include a conductive material, such as acetylene black, being mixed with a bonder and deposited onto the anode current collector.
  • a three-part lithium gel separator layer may be created.
  • the lithium gel separator layer may be in the form of a dry separator layer. That is, liquid electrolyte, such as lithium liquid, has not yet been injected into or permeated throughout the scaffolding layer as detailed in relation to FIG. 3A . In other embodiments, the scaffolding material has been permeated with the liquid.
  • An anti-dendrite layer may be layered onto the lithium gel separator layer, in which the lithium liquid (or another liquid electrolyte) may be present or not yet introduced at block 1020.
  • the anti-dendrite layer may be as detailed in relation to anti-dendrite layer 140 of FIG. 1 .
  • the amount of adhesion between the lithium gel separator layer and the anti-dendrite layer may be greater than the amount of adhesion between the anti-dendrite layer and the interfacial bonding layer.
  • the cathode layer may be layered onto the lithium gel separator layer (of which the gel is either still in the form of a liquid or not yet present).
  • the cathode collector layer may be layered onto the cathode layer. In some embodiments, block 1030 may be performed, then the combined cathode and cathode current collector layers may be layered onto the lithium gel separator layer at block 1025.
  • the anti-dendrite layer that was previously layered onto the lithium-gel separator layer may have its opposite side layers layered onto the interfacial bonding layer.
  • the layering of the anti-dendrite layer and the interfacial bonding layer may result in relatively little adhesion being present between the layers.
  • the anti-dendrite layer creates an interface that has less adhesion with the interfacial bonding layer than the interfacial bonding layer forms with the anode current collector.
  • the amount of adhesion can be controlled by modulating the binder and active conductive material ratio of the interfacial bonding layer.
  • PvDF may be used as the binder and ketchen black may be used as the active material in a ratio of 3% PvDF to 97% ketchen black. In other embodiments, the ration of ketchen black is between 95% and 98%.
  • blocks 1005-1030 may be repeated multiple times to create multiple layer stacks for a solid state battery cell. For instance, 16 sets of layers may be created in a stack set similar to detailed in relation to FIG. 2 with the addition of interfacial bonding layers. Such an arrangement allows for the anode current collector and cathode current collector to be in contact with anti-dendrite layers and cathodes, respectively, on opposite sides.
  • the one or more layer stacks may be packaged in a pouch cell.
  • the lithium liquid (or other form of liquid electrolyte), assuming it was introduced at block 1015, may still be in liquid form.
  • the layers stacks may be vacuum sealed within the pouch cell to remove excess air.
  • the pouch cell may be made of a flexible material, such as plastic, that can allow the pouch to expand and be compressed. If the liquid electrolyte, such as lithium liquid was not permeated throughout the scaffolding layer at block 1015, the liquid electrolyte may be introduced within the pouch cell when packaging is being performed (or before or after) at block 1040. The lithium liquid may then permeate into the scaffolding layer of the dry separator layer.
  • one or more processes of heat, pressure, or both may be applied to the packaged pouch cell.
  • This process can perform multiple functions: 1) block 1045 may increase the amount of physical contact between adjacent layers of the battery cell; 2) block 1045 may cause the liquid electrolyte (e.g., lithium liquid) to convert to a lithium gel; and 3) block 1045 can help create adhesion between the interfacial bonding layers and the anode current collectors that is greater than the amount of adhesion between the anti-dendrite layers and the interfacial bonding layers.
  • pressure may first be applied at room temperature, at a force of between 80 and 120 N/cm 2 for a duration of between 60 and 120 seconds.
  • This portion of the process may increase the amount of contact present at one of more interfaces of the layers of the battery cell.
  • a heat press process may then be performed at a temperature of between 50°C - 130°C at a force of between 100 - 1000 N/cm 2 for a duration of between 60 and 2400 seconds.
  • the pouch cell may be installed within a jig press (or some other mechanical device that applies pressure to the pouch cell).
  • the jig press may be used to apply long-term pressure to the SSB pouch cell.
  • multiple SSB pouch cells are layered and then compressed using the jig press. While in the jig press, the SSB pouch cells may be repeated charged and discharged.
  • the SSB pouch cells may be used to power a vehicle or some other form of electrically-powered device.
  • configurations may be described as a process which is depicted as a flow diagram or block diagram. Although each may describe the operations as a sequential process, many of the operations can be performed in parallel or concurrently. In addition, the order of the operations may be rearranged. A process may have additional steps not included in the figure.

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Claims (15)

  1. Verfahren zur Herstellung einer zylindrischen anodenfreien Anti-Dendrit-Festkörperbatterie, wobei das Verfahren Folgendes umfasst:
    Anbringen einer Kathodenschicht (120) mit einer Kathodenstromkollektorschicht (110);
    Abscheiden einer Grenzflächenschicht (710) auf einer Anodenstromkollektorschicht (150);
    Aufbringen einer Anti-Dendrit-Schicht (140) zwischen der Anodenstromkollektorschicht (150) und der Kathodenschicht (120);
    Erzeugen eines geschichteten Stapels, der eine Trockenseparatorschicht (300), die Kathodenschicht (120), die mit der Kathodenstromkollektorschicht (110) geschichtet ist, und die Anti-Dendrit-Schicht (140), die mit der Anodenstromkollektorschicht (150) geschichtet ist, umfasst, wobei die Trockenseparatorschicht (300) zwischen der Kathodenschicht (120) und der Anti-Dendrit-Schicht (140) angeordnet ist;
    Rollen des geschichteten Stapels zu einer zylindrischen Gelee-Rolle;
    Einführen des gerollten geschichteten Stapels in einen Beutel;
    Permeation einer flüssigen Elektrolytmischung in den Beutel, wobei die flüssige Elektrolytmischung die Trockenseparatorschicht (300) durchdringt und die flüssige Elektrolytmischung ein Salz und ein Lösungsmittel umfasst;
    Ausüben von Druck auf den Beutel nach dem Durchdringen der flüssigen Elektrolytmischung;
    wobei während des Ausübens von Druck auf den Beutel Wärme auf den Beutel ausgeübt wird, wobei:
    die Wärme zumindest teilweise bewirkt, dass die flüssige Elektrolytmischung, die die Trockenseparatorschicht (300) durchdringt, zu einem Gel wird; und
    ein erstes Maß an Adhäsion zwischen der Grenzflächenbindungsschicht (710) und der Anodenstromkollektorschicht (150) größer ist als ein zweites Maß an Adhäsion zwischen der Grenzflächenbindungsschicht (710) und der Anti-Dendrit-Schicht (140);
    Entfernen des gerollten geschichteten Stapels aus dem Beutel nach Anwendung des Drucks und der Wärme; und
    Einsetzen des aus dem Beutel entnommenen gerollten geschichteten Stapels in einen zylindrischen Batteriezellenbehälter.
  2. Verfahren zur Herstellung der zylindrischen anodenfreien Anti-Dendrit-Festkörperbatterie nach Anspruch 1, wobei die flüssige Elektrolytmischung weiter ein Polymeradditiv und ein Vernetzeradditiv umfasst, die bewirken, dass die flüssige Elektrolytmischung zum Gel wird, wenn die Wärme angewendet wird.
  3. Verfahren zur Herstellung der zylindrischen anodenfreien Anti-Dendrit-Festkörperbatterie nach Anspruch 1, wobei eine erste Klebeschicht (310-1) an der Trockenseparatorschicht (300) angebracht ist so dass sich die erste Klebeschicht (310-1) zwischen der Trockenseparatorschicht (300) und der Kathodenschicht (120) befindet.
  4. Verfahren zur Herstellung der zylindrischen anodenfreien Anti-Dendrit-Festkörperbatterie nach Anspruch 3, wobei eine zweite Klebeschicht (310-2) an der Trockenseparatorschicht (300) angebracht ist, so dass sich die zweite Klebeschicht (310-2) zwischen der Trockenseparatorschicht (300) und der Anti-Dendrit-Schicht (140) befindet.
  5. Verfahren zur Herstellung der zylindrischen anodenfreien Anti-Dendrit-Festkörperbatterie nach Anspruch 1, weiter umfassend:
    Einsetzen des Beutels in ein zylindrisches Pressmodul, wobei das zylindrische Pressmodul Folgendes umfasst: ein komprimierbares Material, das um einen gebogenen Rand des Beutels gewickelt ist.
  6. Verfahren zur Herstellung der zylindrischen anodenfreien Anti-Dendrit-Festkörperbatterie nach Anspruch 5, weiter umfassend:
    Einführen einer Temperatursonde zur Überwachung der Temperatur zwischen dem Beutel und dem zylindrischen Pressmodul.
  7. Verfahren zur Herstellung der zylindrischen anodenfreien Anti-Dendrit-Festkörperbatterie nach Anspruch 6, wobei die Wärme durch das komprimierbare Material, das um den gebogenen Rand des Beutels gewickelt ist, zugeführt wird.
  8. Verfahren zur Herstellung der zylindrischen anodenfreien Anti-Dendrit-Festkörperbatterie nach Anspruch 7, wobei die angewandte Hitze zwischen 150 °C und 250 °C liegt.
  9. Verfahren zur Herstellung der zylindrischen anodenfreien Anti-Dendrit-Festkörperbatterie nach Anspruch 1, wobei die Anti-Dendrit-Schicht (140) zwischen 0,05 Mikrometer und 10 Mikrometer dick ist.
  10. Verfahren zur Herstellung der zylindrischen anodenfreien Anti-Dendrit-Festkörperbatterie nach Anspruch 1, wobei die Anti-Dendrit-Schicht (140) ein oder mehrere Materialien umfasst, die ausgewählt sind aus der Gruppe bestehend aus: Ruß; Acetylenschwarz; Ketchenschwarz; Silber; Zink; Gold; Wismut; Zinn; Polyvinylidenfluorid, PVDF; Polymid, PI; Polyacrylsäure, PAA; und Carboxymethylcellulose-Styrol-Butadien-Kautschuk, CMC-SBR.
  11. Zylindrische anodenfreie Anti-Dendrit-Festkörperbatterie, umfassend:
    eine Kathodenschicht (120);
    eine Kathodenstromkollektorschicht (110), die mit der Kathodenschicht (120) verbunden ist;
    eine Anodenstromkollektorschicht (150);
    eine Anti-Dendrit-Schicht (140), die sich zwischen der Anodenstromkollektorschicht (150) und der Kathodenschicht (120) befindet;
    eine Lithiumgel-Separatorschicht (130), die sich zwischen der Kathodenschicht (120) und der Anti-Dendrit-Schicht (140) befindet;
    eine Grenzflächenbindungsschicht (710), die auf der Anodenstromkollektorschicht (150) abgeschieden ist, wobei ein erstes Maß an Adhäsion zwischen der Grenzflächenbindungsschicht (710) und der Anodenstromkollektorschicht (150) größer ist als ein zweites Maß an Adhäsion zwischen der Grenzflächenbindungsschicht (710) und der Anti-Dendrit-Schicht (140); und
    einen Behälter, in den die Kathodenschicht (120), die Kathodenstromkollektorschicht (110), die Anodenstromkollektorschicht (150), die Anti-Dendrit-Schicht (140) und die Lithiumgel-Separatorschicht (130) eingesetzt sind.
  12. Zylindrische anodenfreie Anti-Dendrit-Festkörperbatterie nach Anspruch 11, wobei die Lithiumgel-Separatorschicht (130) Folgendes umfasst: ein Gerüstmaterial (305); ein Lithiumsalz; ein Lösungsmittel; und zwei oder mehr Additive.
  13. Zylindrische anodenfreie Anti-Dendrit-Festkörperbatterie nach Anspruch 12, wobei die zwei oder mehr Additive ein Polymeradditiv und ein Vernetzeradditiv umfassen, wobei das Polymeradditiv und das Vernetzeradditiv bewirken, dass das Lösungsmittel und das Lithiumsalz bei Wärmeeinwirkung ein Gel bilden.
  14. Zylindrische anodenfreie Anti-Dendrit-Festkörperbatterie nach Anspruch 12, wobei die Anti-Dendrit-Schicht (140) ein oder mehrere Materialien umfasst, die aus der Gruppe ausgewählt sind, die aus Ruß; Acetylenschwarz; Ketchenschwarz; Silber; Zink; Gold; Wismut; Zinn; Polyvinylidenfluorid, PVDF; Polymid, PI; Polyacrylsäure, PAA; und Carboxymethylcellulose-Styrol-Butadien-Kautschuk, CMC-SBR, besteht.
  15. Zylindrische anodenfreie Anti-Dendrit-Festkörperbatterie nach Anspruch 11, wobei die Anti-Dendrit-Schicht (140) zwischen 0,05 Mikrometer und 10 Mikrometer dick ist.
EP20754569.0A 2019-07-29 2020-07-28 Zylindrische anodenfreie festkörperbatterie mit einer pseudofesten lithiumgelschicht Active EP4005016B1 (de)

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JP7710736B2 (ja) 2025-07-22
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